Developer for photosensitive resist material and patterning process

ABSTRACT

An aqueous solution containing 0.1-20 wt % of a cyclic ammonium hydroxide is a useful developer for photosensitive resist materials. A resist pattern is formed by applying a chemically amplified positive resist composition onto a substrate to form a resist film, exposing the resist film to high-energy radiation, and developing the exposed resist film in a cyclic ammonium hydroxide-containing aqueous solution.

CROSS-REFERENCE TO RELATED APPLICATION

This non-provisional application claims priority under 35 U.S.C. §119(a) on Patent Application No. 2013-123335 filed in Japan on Jun. 12, 2013, the entire contents of which are hereby incorporated by reference.

TECHNICAL FIELD

This invention relates to a developer for photosensitive resist materials and a patterning process using the same.

BACKGROUND ART

To meet the demand for higher integration density and operating speed of LSIs, the effort to reduce the pattern rule is in rapid progress. The wide-spreading flash memory market and the demand for increased storage capacities drive forward the miniaturization technology. As the advanced miniaturization technology, manufacturing of microelectronic devices at the 65-nm node by the ArF lithography has been implemented in a mass scale. Manufacturing of 45-nm node devices by the next generation ArF immersion lithography is approaching to the verge of high-volume application. The candidates for the next generation 32-nm node include ultra-high NA lens immersion lithography using a liquid having a higher refractive index than water in combination with a high refractive index lens and a high refractive index resist film, extreme ultraviolet (EUV) lithography of 13.5 nm wavelength, and double patterning version of the ArF lithography, on which active research efforts have been made.

With respect to high-energy radiation of very short wavelength such as electron beam (EB) or x-ray, hydrocarbons and similar light elements used in resist materials have little absorption. Then polyhydroxystyrene base resist materials are under consideration. Resist materials for EB lithography are practically used in the mask image writing application. Recently, the mask manufacturing technology becomes of greater interest. Reduction projection exposure systems or steppers have been used since the time when the exposure light was g-line. While their demagnification factor was 1/5, a factor of 1/4 is now used as a result of chip size enlargement and projection lens diameter increase. It becomes of concern that a dimensional error of a mask has an impact on the dimensional variation of a pattern on wafer. It is pointed out that as the pattern feature is reduced, the value of a dimensional variation on the wafer becomes greater than the value of a dimensional error of the mask. This is evaluated by a mask error enhancement factor (MEEF) which is a dimensional variation on wafer divided by a dimensional error of mask. Patterns on the order of 45 nm often show an MEEF in excess of 4. In a situation including a demagnification factor of 1/4 and a MEEF of 4, the mask manufacture needs an accuracy substantially equivalent to that for equi-magnification masks.

The exposure system for mask manufacturing made a transition from the laser beam exposure system to the EB exposure system to increase the accuracy of line width. Since a further size reduction becomes possible by increasing the accelerating voltage of the electron gun in the EB exposure system, the accelerating voltage increased from 10 keV to 30 keV and reached 50 keV in the current mainstream system. A voltage of 100 keV is now under investigation.

As the accelerating voltage increases, a lowering of sensitivity of resist film becomes of concern. As the accelerating voltage increases, the influence of forward scattering in a resist film becomes so reduced that the contrast of electron image writing energy is improved to ameliorate resolution and dimensional control whereas electrons can pass straightforward through the resist film so that the resist film becomes less sensitive. Since the mask exposure tool is designed for exposure by direct continuous writing, a lowering of sensitivity of resist film leads to an undesirably reduced throughput. Due to a need for higher sensitivity, chemically amplified resist compositions are contemplated.

Thinning of resist film is in progress to facilitate reduction of pattern feature in the EB lithography for mask manufacturing and to prevent the pattern from collapsing due to a higher aspect ratio during development. In the case of photolithography, a thinning of resist film greatly contributes to resolution improvement. This is because introduction of chemical mechanical polishing (CMP) or the like has driven forward device planarization. In the case of mask manufacture, substrates are flat, and the thickness of processable substrates (e.g., Cr, MoSi or SiO₂) is predetermined by a percent light shield or phase shift control. The dry etch resistance of resist film must be improved before the film can be reduced in thickness.

It is generally believed that there is a correlation between the carbon density and the dry etch resistance of resist film. For EB writing which is not affected by absorption, resist materials based on novolac resins having better etch resistance have been developed. Indene copolymers described in Patent Document 1 and acenaphthylene copolymers described in Patent Document 2 are expected to have improved etch resistance due to a high carbon density and a robust main chain structure based on cycloolefin structure.

Also, with respect to the soft x-ray (EUV) lithography at wavelength 5-20 nm, the reduced absorption of carbon atoms was reported. Increasing the carbon density is effective not only for improving dry etch resistance, but also for increasing the transmittance in the soft x-ray wavelength region.

As the feature size is reduced, image blurs due to acid diffusion become a problem. To insure resolution for fine patterns with a size of 45 nm et seq., not only an improvement in dissolution contrast is requisite, but control of acid diffusion is also important, as known from previous reports. Since chemically amplified resist compositions are designed such that sensitivity and contrast are enhanced by acid diffusion, an attempt to minimize acid diffusion by reducing the temperature and/or time of post-exposure baking (PEB) fails, resulting in drastic reductions of sensitivity and contrast. Since the distance of acid diffusion is closely related to the type of acid labile group, it would be desirable to have an acid labile group which permits deprotection reaction to proceed at a very short distance of acid diffusion.

A tradeoff among sensitivity, edge roughness and resolution is reported. Increasing sensitivity leads to reductions of edge roughness and resolution. Controlling acid diffusion improves resolution at the sacrifice of edge roughness and sensitivity. Addition of an acid generator capable of generating a bulky acid is effective for suppressing acid diffusion, but leads to reductions of edge roughness and sensitivity as pointed out above. It is then proposed to copolymerize a polymer with an acid generator in the form of an onium salt having polymerizable olefin. Patent Documents 3 to 5 disclose sulfonium salts having polymerizable olefin capable of generating a sulfonic acid and similar iodonium salts. A photoresist using a base polymer having a polymerizable acid generator copolymerized therein exhibits reduced edge roughness due to controlled acid diffusion and uniform dispersion of acid generator within the polymer, succeeding in improving both resolution and edge roughness at the same time.

One serious problem in the EUV lithography is pattern collapse. It is believed in the art that pattern collapse is caused by swell in the developer. For the purpose of reducing swell in tetramethylammonium hydroxide (TMAH) aqueous solution, it is contemplated to use tetrabutylammonium hydroxide (TBAH) aqueous solution as the developer. Since this developer is still insufficient in forming patterns with a feature size of 16 nm or less, there is a need to have a developer capable of preventing swell.

CITATION LIST

Patent Document 1: JP 3865048

Patent Document 2: JP-A 2006-169302

Patent Document 3: JP-A H04-230645

Patent Document 4: JP-A 2005-084365

Patent Document 5: JP-A 2006-045311

Patent Document 6: JP 4771974

Patent Document 7: JP 4900603

DISCLOSURE OF INVENTION

An object of the present invention is to provide a developer which is used in developing a photosensitive resist material to form a resist pattern with minimal edge roughness while preventing pattern collapse or formation of bridge defects between pattern features after development; and a pattern forming process using the developer.

The inventors have found that an aqueous solution of a specific cyclic ammonium hydroxide is an effective developer for use in the development of a photosensitive resist material, typically a chemically amplified positive resist composition comprising a polymer adapted to accelerate alkaline dissolution under the action of acid as a base resin.

In one aspect, the invention provides a developer for photosensitive resist materials comprising a cyclic ammonium hydroxide having the general formula (1):

wherein R¹ and R² each are a straight, branched or cyclic C₁-C₆ alkyl group or C₂-C₁₀ alkenyl or alkynyl group, and R³ is methylene, ethylene, —O—CH₂—, —S—CH₂— or —NH—CH₂—.

Preferably, the cyclic ammonium hydroxide is 1-butyl-1-methylpyrrolidinium hydroxide, 1-propyl-1-methylpyrrolidinium hydroxide, 1-butyl-1-methylpiperidinium hydroxide, 1-propyl-1-methylpiperidinium hydroxide or mepiquathydroxide.

In a preferred embodiment, the developer may further comprise 0.0001 to 5% by weight of an acetylene alcohol having the general formula (AA-1):

wherein R⁴ to R⁷ are each independently C₁-C₂₀ alkyl, R⁸ and R⁹ are each independently C₁-C₁₀ alkylene, a and b are such integers that the sum a+b is 0 to 60.

In another aspect, the invention provides a pattern forming process comprising the steps of providing a chemically amplified positive resist composition adapted to increase an alkali dissolution rate under the action of acid, and developing the resist composition in an aqueous solution containing an ammonium hydroxide of formula (1).

In a preferred embodiment, the chemically amplified positive resist composition comprises a polymer comprising recurring units having an acid labile group and recurring units having a hydroxyl and/or lactone ring adhesive group as a base resin.

More preferably, the polymer has a weight average molecular weight of 1,000 to 500,000, and the recurring units having an acid labile group are recurring units of at least one type selected from recurring units (a1) and (a2) having a carboxyl or phenolic hydroxyl group substituted with an acid labile group, as represented by the general formula (2).

Herein R¹⁰ and R¹² are each independently hydrogen or methyl, R¹¹ and R¹³ each are an acid labile group, Y¹ is a single bond, a divalent C₁-C₁₂ linking group having at least one of ester, lactone ring, phenylene and naphthylene, a phenylene group or a naphthylene group, Y² is a single bond, ester group or amide group, subscripts al and a2 are numbers in the range: 0≦a1≦0.9, 0≦a2≦0.9, and 0<a1+a2<1.0.

In a more preferred embodiment, the polymer comprising recurring units of at least one type selected from recurring units (a1) and (a2) having a carboxyl or phenolic hydroxyl group substituted with an acid labile group, represented by the general formula (2), has further copolymerized therein recurring units of at least one type selected from sulfonium salt units (b1) to (b3), as represented by the general formula (3).

Herein R⁰²⁰, R⁰²⁴, and R⁰²⁸ each are hydrogen or methyl, R is a single bond, phenylene, —O—R⁰³³—, or —C(═O)—Y—R⁰³³—, Y is oxygen or NH, R⁰³³ is a straight, branched or cyclic C₁-C₆ alkylene group, alkenylene group or phenylene group, which may contain a carbonyl (—CO—), ester (—COO—), ether (—O—), or hydroxyl moiety, R⁰²², R⁰²³, R⁰²⁵, R⁰²⁶, R⁰²⁷, R⁰²⁹, R⁰²³⁰, are each independently a straight, branched or cyclic C₁-C₁₂ alkyl group which may contain a carbonyl, ester or ether moiety, a C₆-C₁₂ aryl group, a C₇-C₂₀ aralkyl group, or a thiophenyl group, A¹ is a single bond, -A⁰-C(═O)—O—, -A⁰-O— or -A⁰-O—C(═O)—, A⁰ is a straight, branched or cyclic C₁-C₁₂ alkylene group which may contain a carbonyl, ester or ether moiety, A² is hydrogen, CF₃ or carbonyl, Z¹ is a single bond, methylene, ethylene, phenylene, fluorinated phenylene, —O—R⁰³²—, or —C(═O)—Z²—R⁰³²—, Z² is oxygen or NH, R⁰³² is a straight, branched or cyclic C₁-C₆ alkylene, phenylene, fluorinated phenylene, trifluoromethyl-substituted phenylene or alkenylene group, which may contain a carbonyl, ester, ether or hydroxyl moiety, M⁻ is a non-nucleophilic counter ion, subscripts b1, b2 and b3 are numbers in the range: 0≦b1≦0.3, 0≦b2≦0.3, 0≦b3≦0.3, and 0<b1+b2+b3≦0.3.

In a preferred embodiment, the resist composition may further comprise at least one of an organic solvent, basic compound, dissolution regulator, and surfactant.

The pattern forming process may comprise the steps of applying the resist composition onto a substrate to form a coating, baking, exposing the coating to high-energy radiation, and developing the exposed coating in the developer defined above. Typically, the high-energy radiation is KrF excimer laser of wavelength 248 nm, ArF excimer laser of wavelength 193 nm, electron beam or soft x-ray of wavelength 3 to 15 nm.

Advantageous Effects of Invention

When a resist film of photosensitive resist material, typically chemically amplified positive resist composition is developed in the developer of the invention, any swell of the resist film during development is suppressed. Thus a resist pattern with minimal edge roughness can be formed while preventing pattern collapse or bridge defect formation.

DESCRIPTION OF EMBODIMENTS

The singular forms “a,” “an” and “the” include plural referents unless the context clearly dictates otherwise. “Optional” or “optionally” means that the subsequently described event or circumstances may or may not occur, and that description includes instances where the event or circumstance occurs and instances where it does not. The terminology “C_(x)-C_(y)”, as applied to a particular unit, such as, for example, a chemical substituent group, means having a carbon atom content of from “x” carbon atoms to “y” carbon atoms per such unit.

The abbreviations have the following meaning.

-   EB: electron beam -   EUV: extreme ultraviolet -   PAG: photoacid generator -   PEB: post-exposure bake -   LWR: line width roughness -   Mw: weight average molecular weight -   Mn: number average molecular weight -   Mw/Mn: dispersity or average molecular weight distribution -   GPC: gel permeation chromatography

The inventors have found that when an aqueous solution containing 0.1 to 20% by weight of a cyclic ammonium hydroxide is applied as the developer to a photosensitive resist material, typically a positive resist composition comprising a base polymer adapted to accelerate alkaline dissolution under the action of acid, pattern collapse or bridge defect formation during development is suppressed.

Specifically, in one aspect of the invention, an aqueous solution containing 0.1 to 20% by weight of a cyclic ammonium hydroxide having the general formula (1) is applied as the developer to a chemically amplified positive resist composition comprising a polymer adapted to accelerate alkaline dissolution under the action of acid as base resin.

Herein R¹ and R² each are a straight, branched or cyclic C₁-C₆ alkyl group or a C₂-C₁₀ alkenyl or alkynyl group, and R³ is methylene, ethylene, —O—CH₂—, —S—CH₂— or —NH—CH₂—.

Illustrative, non-limiting examples of the cyclic ammonium hydroxide having formula (1) are shown below.

Of these, 1-butyl-1-methylpyrrolidinium hydroxide, 1-propyl-1-methylpyrrolidinium hydroxide, 1-butyl-1-methylpiperidinium hydroxide, 1-propyl-1-methylpiperidinium hydroxide, and mepiquathydroxide are most preferred.

Where the anion to the quaternary ammonium in the cyclic ammonium represented by formula (1) is a halogen atom such as chlorine, bromine or iodine, it is converted to a hydroxyl group by ion exchange.

In general, tetramethylammonium hydroxide (TMAH) is used as the aqueous alkaline developer. While potassium hydroxide was used as the developer in the past, the alkali metal was found to have adverse impact on device operation. Since then, quaternary ammonium hydroxy salts have been used. Besides the TMAH, suitable quaternary ammonium salts include tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide (TPAH), tetrabutylammonium hydroxide (TPAH), tetrapentylammonium hydroxide, tributylmethylammonium hydroxide, trimethylhydroxyethylammonium hydroxide (also known as “choline”), tetraethanolammonium hydroxide, and methyltriethanolammonium hydroxide.

In the lithography art, aqueous TMAH solution is widely used as the developer. However, the TMAH solution suffers from the problem of pattern collapse due to swell particularly when applied to polymethacrylate-based resists adapted to generate carboxylic acid after deprotection. A study is thus made on an alkyl group of longer chain, specifically tetrabutylammonium hydroxide (TBAH). A longer alkyl chain leads to a molecular weight buildup, which is effective for inhibiting the penetration of the developer into the resist film. This, in turn, suppresses swell and mitigates pattern collapse. However, the TBAH developer still fails to prevent pattern collapse when it is intended to form a line pattern with a feature size of less than 20 nm.

When an aqueous solution containing a specific cyclic alkyl ammonium hydroxide is used as the developer, any swell of the base resin in the developer is minimized as compared with the chainlike tetraalkylammonium hydroxides. Thus pattern collapse and bridge defects are suppressed. The concentration of cyclic ammonium hydroxide in the aqueous solution is 0.1 to 10% by weight, preferably 0.5 to 8% by weight, and more preferably 1.0 to 7% by weight.

In addition to the optionally substituted cyclic alkyl ammonium hydroxide, the aqueous solution may further contain 0.0001 to 5% by weight of an acetylene alcohol having the general formula (AA-1):

wherein R⁴ to R⁷ are each independently C₁-C₂₀ alkyl, R⁸ and R⁹ are each independently C₁-C₁₀ alkylene, a and b are such integers that the sum a+b is 0 to 60.

The acetylene alcohol is commercially available, for example, under the trade name of Surfynol® 104 series and 400 series from Nissin Chemical Co., Ltd.

The concentration of acetylene alcohol in the aqueous solution is 0.0001 to 5% by weight, preferably 0.001 to 3% by weight, and more preferably 0.01 to 1% by weight. The acetylene alcohol has both functions of defoaming and surface activation. If micro-bubbles are present in the developer, those portions of the resist surface in contact with micro-bubbles are not developed, resulting in development defects. A defoamer is necessary to eliminate micro-bubbles. Since water has a high surface tension, the resist surface is hardly wetted. The surface tension must be reduced in order that the resist surface be readily wetted. Addition of a surfactant is effective to this end. The addition of a common surfactant is effective for reducing surface tension, but facilitates foaming. It is an acetylene alcohol that is effective for reducing surface tension and suppressing foaming.

The photoresist material used in the pattern forming process of the invention is a chemically amplified positive resist composition, typically comprising a polymer comprising recurring units having an acid labile group as a base resin. In a preferred embodiment, the polymer comprises recurring units (a1) and/or (a2) having a carboxyl or phenolic hydroxyl group whose hydrogen atom is substituted by an acid labile group, as represented by the general formula (2).

Herein R¹⁰ and R¹² are each independently hydrogen or methyl, R¹¹ and R¹³ each are an acid labile group, Y¹ is a single bond, a divalent C₁-C₁₂ linking group having at least one of ester, lactone ring, phenylene and naphthylene, a phenylene group or a naphthylene group, Y² is a single bond, ester group or amide group, a1 and a2 are numbers in the range: 0≦a1≦0.9, 0≦a2≦0.9, and 0<a1+a2<1.0.

Of the recurring units in the polymer, those recurring units having an acid labile group, represented by recurring units (a1) in formula (2) are units having a carboxyl group whose hydrogen atom is substituted by an acid labile group, specifically the hydrogen atom of hydroxyl of (meth)acrylate is substituted by an acid labile group. Examples of the monomer from which recurring units (a1) are derived are shown below.

Herein R¹⁰ is hydrogen or methyl, and R¹¹ is an acid labile group.

Those recurring units having an acid labile group, represented by recurring units (a2) in formula (2) are units having a phenolic hydroxyl group whose hydrogen atom is substituted by an acid labile group, preferably the hydrogen atom of hydroxyl of hydroxystyrene or hydroxyphenyl (meth)acrylate is substituted by an acid labile group. Examples of the monomer from which recurring units (a2) are derived are shown below.

Herein R¹² is hydrogen or methyl, and R¹³ is an acid labile group.

The acid labile groups represented by R¹¹ and R¹³ in formula (2) may be selected from a variety of such groups.

The acid labile groups may be the same or different and preferably include groups of the following formulae (A-1) to (A-3).

In formula (A-1), R³⁰° is a tertiary alkyl group of 4 to 20 carbon atoms, preferably 4 to 15 carbon atoms, a trialkylsilyl group in which each alkyl moiety has 1 to 6 carbon atoms, an oxoalkyl group of 4 to 20 carbon atoms, or a group of formula (A-3). Exemplary tertiary alkyl groups are tert-butyl, tert-amyl, 1,1-diethylpropyl, 1-ethylcyclopentyl, 1-butylcyclopentyl, 1-ethylcyclohexyl, 1-butylcyclohexyl, 1-ethyl-2-cyclopentenyl, 1-ethyl-2-cyclohexenyl, and 2-methyl-2-adamantyl. Exemplary trialkylsilyl groups are trimethylsilyl, triethylsilyl, and dimethyl-tert-butylsilyl.

Exemplary oxoalkyl groups are 3-oxocyclohexyl, 4-methyl-2-oxooxan-4-yl, and 5-methyl-2-oxooxolan-5-yl. Letter A1 is an integer of 0 to 6.

In formula (A-2), R³¹ and R³² each are hydrogen or a straight, branched or cyclic alkyl group of 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms. Exemplary alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, cyclopentyl, cyclohexyl, 2-ethylhexyl, and n-octyl. R³³ is a monovalent hydrocarbon group of 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, which may contain a heteroatom such as oxygen, examples of which include straight, branched or cyclic alkyl groups and substituted forms of such alkyl groups in which some hydrogen atoms are replaced by hydroxyl, alkoxy, oxo, amino, alkylamino or the like. Illustrative examples of the substituted alkyl groups are shown below.

A pair of R³¹ and R³², R³¹ and R³³, or R³² and R³³ may bond together to form a ring with the carbon and oxygen atoms to which they are attached. Each of R³¹, R³² and R³³ is a straight or branched alkylene group of 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms when they form a ring, while the ring preferably has 3 to 10 carbon atoms, more preferably 4 to 10 carbon atoms.

Examples of the acid labile groups of formula (A-1) include tert-butoxycarbonyl, tert-butoxycarbonylmethyl, tert-amyloxycarbonyl, tert-amyloxycarbonylmethyl, 1,1-diethylpropyloxycarbonyl, 1,1-diethylpropyloxycarbonylmethyl, 1-ethyl cyclopentyloxycarbonyl, 1-ethylcyclopentyloxycarbonylmethyl, 1-ethyl-2-cyclopentenyloxycarbonyl, 1-ethyl-2-cyclopentenyloxycarbonylmethyl, 1-ethoxyethoxycarbonylmethyl, 2-tetrahydropyranyloxycarbonylmethyl, and 2-tetrahydrofuranyloxycarbonylmethyl groups.

Also included are substituent groups having the formulae (A-1)-1 to (A−1)-10.

Herein R³⁷ is each independently a straight, branched or cyclic C₁-C₁₀ alkyl group or C₆-C₂₀ aryl group. R³⁸ is hydrogen or a straight, branched or cyclic C₁-C₁₀ alkyl group. R³⁹ is each independently a straight, branched or cyclic C₂-C₁₀ alkyl group or C₆-C₂₀ aryl group. A1 is an integer of 0 to 6.

Of the acid labile groups of formula (A-2), the straight and branched ones are exemplified by the following groups having formulae (A-2)-1 to (A-2)-69.

Of the acid labile groups of formula (A-2), the cyclic ones are, for example, tetrahydrofuran-2-yl, 2-methyltetrahydrofuran-2-yl, tetrahydropyran-2-yl, and 2-methyltetrahydropyran-2-yl.

Other examples of acid labile groups include those of the following formula (A-2a) or (A-2b) while the polymer may be crosslinked within the molecule or between molecules with these acid labile groups.

Herein R⁴⁰ and R⁴¹ each are hydrogen or a straight, branched or cyclic C₁-C₈ alkyl group, or R⁴⁰ and R⁴¹, taken together, may form a ring with the carbon atom to which they are attached, and R⁴⁰ and R⁴¹ are straight or branched C₁-C₈ alkylene groups when they form a ring. R⁴² is a straight, branched or cyclic C₁-C₁₀ alkylene group. Each of B1 and D1 is 0 or an integer of 1 to 10, preferably 0 or an integer of 1 to 5, and C1 is an integer of 1 to 7. “A” is a (C1+1)-valent aliphatic or alicyclic saturated hydrocarbon group, aromatic hydrocarbon group or heterocyclic group having 1 to 50 carbon atoms, which may be separated by a heteroatom or in which some hydrogen atoms attached to carbon atoms may be substituted by hydroxyl, carboxyl, carbonyl groups or fluorine atoms. “B” is —CO—O—, —NHCO—O— or —NHCONH—.

Preferably, “A” is selected from divalent to tetravalent, straight, branched or cyclic C₁-C₂₀ alkylene, alkyltriyl and alkyltetrayl groups, and C₆-C₃₀ arylene groups, which may contain a heteroatom or in which some hydrogen atoms attached to carbon atoms may be substituted by hydroxyl, carboxyl, acyl groups or halogen atoms. The subscript C1 is preferably an integer of 1 to 3.

The crosslinking acetal groups of formulae (A-2a) and (A-2b) are exemplified by the following formulae (A-2)-70 through (A-2)-77.

In formula (A-3), R³⁴, R³⁵ and R³⁶ each are a monovalent hydrocarbon group, typically a straight, branched or cyclic C₁-C₂₀ alkyl group, straight, branched or cyclic C₂-C₂₀ alkenyl group or C₆-C₂₀ aryl group, which may contain a heteroatom such as oxygen, sulfur, nitrogen or fluorine. A pair of R³⁴ and R³⁵, R³⁴ and R³⁶, or R³⁵ and R³⁶ may bond together to form a C₃-C₂₀ aliphatic ring with the carbon atom to which they are attached.

Exemplary tertiary alkyl groups of formula (A-3) include tert-butyl, triethylcarbyl, 1-ethylnorbornyl, 1-methylcyclohexyl, 1-ethylcyclopentyl, 2-(2-methyl)adamantyl, 2-(2-ethyl)adamantyl, and tert-amyl.

Other exemplary tertiary alkyl groups include those of the following formulae (A-3)-1 to (A-3)-18.

Herein R⁴³ is each independently a straight, branched or cyclic C₁-C₈ alkyl group or C₆-C₂₀ aryl group, typically phenyl, R⁴⁴ and R⁴⁶ each are hydrogen or a straight, branched or cyclic C₁-C₂₀ alkyl group, and R⁴⁵ is a C₆-C₂₀ aryl group, typically phenyl.

The polymer may be crosslinked within the molecule or between molecules with groups having R⁴⁷ which is a di- or multi-valent alkylene or arylene group, as shown by the following formulae (A-3)-19 and (A-3)-20.

Herein R⁴³ is as defined above, R⁴⁷ is a straight, branched or cyclic C₁-C₂₀ alkylene group or arylene group, typically phenylene, which may contain a heteroatom such as oxygen, sulfur or nitrogen, and E1 is an integer of 1 to 3.

Of recurring units having acid labile groups of formula (A-3), recurring units of (meth)acrylate having an exo-form structure represented by the formula (A-3)-21 are preferred.

Herein, R¹⁰ and a1 are as defined above. R^(c3) is a straight, branched or cyclic C₁-C₈ alkyl group or an optionally substituted C₆-C₂₀ aryl group. R^(c4) to R^(c9), R^(c12) and R^(c13) are each independently hydrogen or a monovalent C₁-C₁₅ hydrocarbon group which may contain a heteroatom. R^(c10) and R^(c11) each are hydrogen or a monovalent C₁-C₁₅ hydrocarbon group which may contain a heteroatom. Alternatively, a pair of R^(c4) and R^(c5), R^(c6) and R^(c8), R^(c6) and R^(c9), R^(c7) and R^(c9), R^(c7) and R^(c13), R^(c8) and R^(c12), R^(c10) and R^(c11), or R^(c11) and R^(c12), taken together, may form a ring, and in that event, each ring-forming R is a divalent C₁-C₁₅ hydrocarbon group which may contain a heteroatom. Also, a pair of R^(c4) and R^(c13), R^(c10) and R^(c13), or R^(c6) and R^(c8) which are attached to vicinal carbon atoms may bond together directly to form a double bond. The formula also represents an enantiomer.

The ester form monomers from which recurring units having an exo-form structure represented by formula (A-3)-21 are derived are described in U.S. Pat. No. 6,448,420 (JP-A 2000-327633). Illustrative non-limiting examples of suitable monomers are given below.

Also included in the acid labile groups of formula (A-3) are acid labile groups of (meth)acrylate having furandiyl, tetrahydrofurandiyl or oxanorbornanediyl as represented by recurring units (a1) of the following formula (A-3)-22.

Herein, R¹⁰ and a1 are as defined above. R^(c14) and R^(c15) are each independently a monovalent, straight, branched or cyclic C₁-C₁₀ hydrocarbon group, or R^(c14) and R^(c15), taken together, may form an aliphatic hydrocarbon ring with the carbon atom to which they are attached. R^(c16) is a divalent group selected from furandiyl, tetrahydrofurandiyl and oxanorbornanediyl. R^(c17) is hydrogen or a monovalent, straight, branched or cyclic C₁-C₁₀ hydrocarbon group which may contain a heteroatom.

Examples of the monomers from which the recurring units substituted with acid labile groups having furandiyl, tetrahydrofurandiyl and oxanorbornanediyl are derived are shown below. Note that Me is methyl and Ac is acetyl.

In the recurring unit (a1), R¹¹ may be an acid labile group having the general formula (A-3)-23.

Herein R²³⁻¹ is hydrogen, C₁-C₄ alkyl, alkoxy, alkanoyl, alkoxycarbonyl, C₆-C₁₀ aryl, halogen, or cyano group, and m23 is an integer of 1 to 4.

Examples of the monomer from which recurring units (a1) substituted with an acid labile group of formula (A-3)-23 are derived are given below.

In the recurring unit (a1), R¹¹ may be an acid labile group having the general formula (A-3)-24.

Herein R²⁴⁻¹ and R²⁴⁻² each are hydrogen, C₁-C₄ alkyl, alkoxy, alkanoyl, alkoxycarbonyl, hydroxyl, C₆-C₁₀ aryl, halogen, or cyano group; R is hydrogen, a straight, branched or cyclic C₁-C₁₂ alkyl group which may contain an oxygen or sulfur atom, C₂-C₁₂ alkenyl, C₂-C₁₂ alkynyl, or C₆-C₁₀ aryl group; R²⁴⁻³, R²⁴⁻⁴, R²⁴⁻⁵, and R²⁴⁻⁶ each are hydrogen, or a pair of R²⁴⁻³ and R²⁴⁻⁴, R²⁴⁻⁴ and R²⁴⁻⁵, or R²⁴⁻⁵ and R²⁴⁻⁶ may bond together to form a benzene ring; m24 and n24 each are an integer of 1 to 4.

Examples of the monomer from which recurring units (a1) substituted with an acid labile group of formula (A-3)-24 are derived are given below.

In the recurring unit (a1), R¹¹ may be an acid labile group having the general formula (A-3)-25.

Herein R²⁵⁻¹ is each independently hydrogen or a straight, branched or cyclic C₁-C₆ alkyl group, and in case m25 is 2 or more, R²⁵⁻¹ may bond together to form a non-aromatic ring of 2 to 8 carbon atoms; the circle denotes a link between carbons C_(A) and C_(B), selected from among ethylene, propylene, butylene and pentylene; R²⁵⁻¹ is not hydrogen when the circle denotes ethylene or propylene; R²⁵⁻² is C₁-C₄ alkyl, alkoxy, alkanoyl, alkoxycarbonyl, hydroxyl, nitro, C₆-C₁₀ aryl, halogen, or cyano group; R is as defined above in formula (A-3)-24; m25 and n25 each are an integer of 1 to 4.

Examples of the monomer from which recurring units (a1) substituted with an acid labile group of formula (A-3)-25 are derived are given below.

In the recurring unit (a1), R¹¹ may be an acid labile group having the general formula (A-3)-26.

Herein R²⁶⁻¹ and R²⁶⁻² each are hydrogen, C₁-C₄ alkyl, alkoxy, alkanoyl, alkoxycarbonyl, hydroxyl, nitro, C₆-C₁₀ aryl, halogen, or cyano group; R is as defined above in formula (A-3)-24; and m26 and n26 each are an integer of 1 to 4.

Examples of the monomer from which recurring units (a1) substituted with an acid labile group of formula (A-3)-26 are derived are given below.

In the recurring unit (a1), R¹¹ may be an acid labile group having the general formula (A-3)-27.

Herein R²⁷⁻¹ and R²⁷⁻² each are hydrogen, C₁-C₄ alkyl, alkoxy, alkanoyl, alkoxycarbonyl, hydroxyl, C₆-C₁₀ aryl, halogen, or cyano group; R is as defined above in formula (A-3)-24; J is methylene, ethylene, vinylene or —CH₂—S—; and m27 and n27 each are an integer of 1 to 4.

Examples of the monomer from which recurring units (a1) substituted with an acid labile group of formula (A-3)-27 are derived are given below.

In the recurring unit (a1), R¹¹ may be an acid labile group having the general formula (A-3)-28.

Herein R²⁸⁻¹ and R²⁸⁻² each are hydrogen, C₁-C₄ alkyl, alkoxy, alkanoyl, alkoxycarbonyl, hydroxyl, C₆-C₁₀ aryl, halogen, or cyano group; R is as defined above in formula (A-3)-24; K is carbonyl, ether, sulfide, —S(═O)— or —S(═O)₂—; and m28 and n28 each are an integer of 1 to 4.

Examples of the monomer from which recurring units (a1) substituted with an acid labile group of formula (A-3)-28 are derived are given below.

In a preferred embodiment, the polymer may have copolymerized therein recurring units (b1), (b2) or (b3) having a sulfonium salt, represented by the following formula (3). A resist composition comprising such a polymer having an acid generator bound to its main chain as base resin has the advantage that the pattern obtained after development has a reduced edge roughness (LWR).

Herein R⁰²⁰, R⁰²⁴, and R⁰²⁸ each are hydrogen or methyl. R⁰²¹ is a single bond, phenylene, —O—R⁰³³—, or —C(═O)—Y—R⁰³³—, wherein Y is oxygen or NH, and R⁰³³ is a straight, branched or cyclic C₁-C₆ alkylene group, alkenylene or phenylene group, which may contain a carbonyl (—CO—), ester (—COO—), ether (—O—) or hydroxyl moiety. R⁰²², R⁰²³, R⁰²⁵, R⁰²⁶, R⁰²⁷, R⁰²⁹, R⁰³⁰, and R⁰³¹ are each independently a straight, branched or cyclic C₁-C₁₂ alkyl group which may contain a carbonyl, ester or ether moiety, or a C₆-C₁₂ aryl, C₇-C₂₀ aralkyl, or thiophenyl group. A¹ is a single bond, -A⁰-C(═O)—O—, -A⁰-O— or -A⁰-O—C(═O)—, wherein A⁰ is a straight, branched or cyclic C₁-C₁₂ alkylene group which may contain a carbonyl, ester or ether moiety. A² is hydrogen, CF₃ or carbonyl. Z¹ is a single bond, methylene, ethylene, phenylene, fluorophenylene, —O—R⁰³²—, or —C(═O)—Z²—R⁰³²—, wherein Z² is oxygen or NH, and R⁰³² is a straight, branched or cyclic C₁-C₆ alkylene, phenylene, fluorophenylene, trifluoromethyl-substituted phenylene or alkenylene group, which may contain a carbonyl, ester, ether or hydroxyl moiety. M⁻ is a non-nucleophilic counter ion. Molar fractions b1, b2 and b3 are in the range of 0≦b1≦0.3, 0≦b2≦0.3, 0≦b3≦0.3, and 0≦b1+b2+b3≦0.3.

Examples of the monomer from which sulfonium salt-containing recurring units (b1) in formula (3) are derived are given below.

Herein M⁻ is a non-nucleophilic counter ion.

Examples of the non-nucleophilic counter ion represented by M⁻ include halide ions such as chloride and bromide ions; fluoroalkylsulfonate ions such as triflate, 1,1,1-trifluoroethanesulfonate, and nonafluorobutanesulfonate; arylsulfonate ions such as tosylate, benzenesulfonate, 4-fluorobenzenesulfonate, and 1,2,3,4,5-pentafluorobenzenesulfonate; alkylsulfonate ions such as mesylate and butanesulfonate; imidates such as bis(trifluoromethylsulfonyl)imide, bis(perfluoroethylsulfonyl)imide and bis(perfluorobutylsulfonyl)imide; methidates such as tris(trifluoromethylsulfonyl)methide and tris(perfluoroethylsulfonyl)methide.

Other non-nucleophilic counter ions include sulfonates having fluorine substituted at α-position as represented by the general formula (K-1) and sulfonates having fluorine substituted at α- and β-positions as represented by the general formula (K-2).

In formula (K-1), R¹⁰² is hydrogen, or a straight, branched or cyclic C₁-C₂₀ alkyl group, C₂-C₂₀ alkenyl group, or C₆-C₂₀ aryl group, which may have an ether, ester, carbonyl moiety, lactone ring or fluorine. In formula (K-2), R¹⁰³ is hydrogen, or a straight, branched or cyclic C₁-C₃₀ alkyl or acyl group, C₂-C₂₀ alkenyl group, or C₆-C₂₀ aryl or aryloxy group, which may have an ether, ester, carbonyl moiety or lactone ring.

Examples of the monomer from which sulfonium salt-containing recurring units (b2) in formula (3) are derived are given below.

Examples of the monomer from which sulfonium salt-containing recurring units (b3) in formula (3) are derived are given below.

While the base resin in the resist composition used in the pattern forming process of the invention is a polymer comprising essentially recurring units (a1) having a carboxyl group substituted with an acid labile group and/or recurring units (a2) having a phenolic hydroxyl group substituted with an acid labile group and optionally recurring units (b1), (b2) or (b3) having an acid generator or sulfonic acid sulfonium salt bound to the main chain, the polymer may have further copolymerized therein recurring units (c) having a phenolic hydroxyl group as adhesive group.

Examples of the monomer from which recurring units (c) having a phenolic hydroxyl group are derived are shown below.

Furthermore, recurring units (d) having another adhesive group may be copolymerized. Suitable other adhesive groups include hydroxyl, carboxyl, lactone ring, carbonate, thiocarbonate, carbonyl, cyclic acetal, ether, ester, sulfonic acid ester, cyano, amide, and —O—C(═O)-G- wherein G is sulfur or NH. It is noted that the aforementioned recurring units having hydroxyl are excluded from units (d). Inter alia, recurring units having lactone ring as the adhesive group are most preferred.

Examples of the monomer from which recurring units (d) having another adhesive group are derived are shown below.

In the case of a monomer having a hydroxyl group, the hydroxyl group may be replaced by an acetal group susceptible to deprotection with acid, typically ethoxyethoxy, prior to polymerization, and the polymerization be followed by deprotection with weak acid and water. Alternatively, the hydroxyl group may be replaced by an acetyl, formyl, pivaloyl or similar group prior to polymerization, and the polymerization be followed by alkaline hydrolysis.

In the polymer, any of indene, benzofuran, benzothiophene, acenaphthylene, chromone, coumarin, norbornadiene and derivatives thereof may be copolymerized as recurring unit (e). Illustrative examples of these compounds are shown below.

Furthermore, any of styrene, vinylnaphthalene, vinylanthracene, vinylpyrene, and methyleneindane may be copolymerized as recurring unit (f).

In the resist polymer, recurring units (a1), (a2), (b1), (b2), (b3), (c), (d), (e) and (f) may be incorporated in the following molar fraction:

-   0≦a1<1.0, 0≦a2<1.0, 0<a1+a2<1.0, -   0≦b1≦0.3, 0≦b2≦0.3, 0≦b3≦0.3, 0≦b1+b2+b3≦0.3, -   0≦c<1.0, 0≦d<1.0, 0<c+d<1.0, 0≦e<1.0, 0≦f<1.0, and -   0.7≦a1+a2+b1+b2+b3+c+d≦1.0; -   preferably 0≦a1≦0.8, 0≦a2≦0.8, 0.1≦a1+a2≦0.8, 0≦b1≦0.3, 0≦b2≦0.3,     0≦b3≦0.3, 0≦b1+b2+b3≦0.3, 0≦c≦0.8, 0≦d≦0.8, 0.2≦c+d≦0.9, 0≦e≦0.5,     0≦f≦0.5, and -   0.8≦a1+a2+b1+b2+b3+c+d≦1.0; -   more preferably 0≦a1≦0.7, 0≦a2≦0.7, 0.1≦a1+a2≦0.7, 0≦b1≦0.3,     0≦b2≦0.3, 0≦b3≦0.3, 0.02≦b1+b2+b3≦0.3, 0≦c≦0.7, 0≦d≦0.7,     0.28≦c+d≦0.88, 0≦e≦0.4, 0≦f≦0.4, and -   0.85≦a1+a2+b1+b2+b3+c+d≦1.0; -   provided that a1+a2+b1+b2+b3+c+d+e+f=1.0.

The polymer may be synthesized by any desired methods, for example, by dissolving suitable monomers corresponding to recurring units (a1) and/or (a2) and optionally recurring units (b1), (b2), (b3), (c), (d), (e) and (f) in an organic solvent, adding a radical polymerization initiator thereto, and effecting heat polymerization. Examples of the organic solvent which can be used for polymerization include toluene, benzene, tetrahydrofuran, diethyl ether, and dioxane. Examples of the polymerization initiator used herein include 2,2′-azobisisobutyronitrile (AIBN), 2,2′-azobis(2,4-dimethyl-valeronitrile), dimethyl 2,2-azobis(2-methylpropionate), benzoyl peroxide, and lauroyl peroxide. Preferably the system is heated at 50 to 80° C. for polymerization to take place. The reaction time is 2 to 100 hours, preferably 5 to 20 hours.

When hydroxystyrene or hydroxyvinylnaphthalene is copolymerized, an alternative method is possible. Specifically, acetoxystyrene or acetoxyvinylnaphthalene is used instead of hydroxystyrene or hydroxyvinylnaphthalene, and after polymerization, the acetoxy group is deprotected by alkaline hydrolysis as mentioned above, for thereby converting the polymer product to polyhydroxystyrene or hydroxypolyvinylnaphthalene. For alkaline hydrolysis, a base such as aqueous ammonia or triethylamine may be used. The reaction temperature is −20° C. to 100° C., preferably 0° C. to 60° C., and the reaction time is 0.2 to 100 hours, preferably 0.5 to 20 hours.

The polymer serving as the base resin in the resist composition should desirably have a weight average molecular weight (Mw) in the range of 1,000 to 500,000, and more desirably 2,000 to 30,000, as measured by GPC versus polystyrene standards. With a Mw of 1,000 or higher, the resist composition becomes heat resistant. A polymer with a Mw of 500,000 or lower does not lose alkaline solubility or give rise to a footing phenomenon after pattern formation.

If a multi-component polymer has a wide molecular weight distribution or dispersity (Mw/Mn), which indicates the presence of lower and higher molecular weight polymer fractions, there is a possibility that foreign matter is left on the pattern or the pattern profile is degraded. The influences of molecular weight and dispersity become stronger as the pattern rule becomes finer. Therefore, the multi-component copolymer should preferably have a narrow dispersity (Mw/Mn) of 1.0 to 2.0, especially 1.0 to 1.5, in order to provide a resist composition suitable for micropatterning to a small feature size.

The polymer is advantageously used as a base resin in a positive resist composition, typically chemically amplified positive resist composition. Specifically, the polymer is used as a base resin and combined with any desired components including an organic solvent, acid generator, dissolution regulator, basic compound, surfactant, and acetylene alcohol to formulate a positive resist composition. This positive resist composition has a very high sensitivity in that the dissolution rate in developer of the polymer in exposed areas is accelerated by catalytic reaction. In addition, the resist film has a high dissolution contrast, resolution, exposure latitude, and process adaptability, and provides a good pattern profile after exposure, yet better etching resistance, and minimal proximity bias because of restrained acid diffusion. By virtue of these advantages, the composition is fully useful in commercial application and suited as a pattern-forming material for the fabrication of VLSIs or photomasks.

Particularly when an acid generator is added to formulate a chemically amplified positive resist composition capable of utilizing acid catalyzed reaction, the composition has a higher sensitivity and is further improved in the properties described above. Typical of the acid generator used herein is a photoacid generator (PAG) capable of generating an acid in response to actinic light or radiation. It is any compound capable of generating an acid upon exposure to high-energy radiation. Suitable PAGs include sulfonium salts, iodonium salts, sulfonyldiazomethane, N-sulfonyloxyimide, and oxime-O-sulfonate acid generators. The acid generators may be used alone or in admixture of two or more. Exemplary acid generators are described in U.S. Pat. No. 7,537,880 (JP-A 2008-111103, paragraphs [0122] to [0142]). Understandably, the acid generator may be omitted when a polymer having recurring units (b1) to (b3) copolymerized therein is used as the base resin.

Examples of the organic solvent used herein are described in JP-A 2008-111103, paragraphs [0144] to [0145] (U.S. Pat. No. 7,537,880). Specifically, exemplary solvents include ketones such as cyclohexanone, cyclopentanone and methyl-2-n-amyl ketone; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and 1-ethoxy-2-propanol; ethers such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, and diethylene glycol dimethyl ether; esters such as propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, and propylene glycol mono-tert-butyl ether acetate; and lactones such as γ-butyrolactone, and mixtures thereof.

Exemplary basic compounds are described in JP-A 2008-111103, paragraphs [0146] to [0164], for example, primary, secondary and tertiary amine compounds, specifically amine compounds having a hydroxyl, ether, ester, lactone, cyano or sulfonate group. Exemplary surfactants are described in JP-A 2008-111103, paragraphs [0165] to [0166]. Exemplary dissolution regulators are described in JP-A 2008-122932 (US 2008090172), paragraphs [0155] to [0178], and exemplary acetylene alcohols in paragraphs [0179] to [0182]. Also useful are quenchers of polymer type as described in JP-A 2008-239918. The polymeric quencher segregates at the resist surface after coating and thus enhances the rectangularity of resist pattern. When a protective film is applied as is often the case in the immersion lithography, the polymeric quencher is also effective for preventing any film thickness loss of resist pattern or rounding of pattern top.

An appropriate amount of the acid generator used is 0.01 to 100 parts, and preferably 0.1 to 80 parts. An appropriate amount of the organic solvent used is 50 to 10,000 parts, especially 100 to 5,000 parts. The dissolution regulator may be blended in an amount of 0 to 50 parts, preferably 0 to 40 parts, the basic compound in an amount of 0 to 100 parts, preferably 0.001 to 50 parts, and the surfactant in an amount of 0 to 100 parts, preferably 0.0001 to 5 parts. All amounts are expressed in parts by weight relative to 100 parts by weight of the base resin.

Process

The positive resist composition, typically chemically amplified positive resist composition comprising an acid labile group-containing polymer having formula (2), an acid generator, and a basic compound in an organic solvent is used in the fabrication of various integrated circuits. Pattern formation using the resist composition may be performed by well-known lithography processes. The process generally involves coating, prebake, exposure, bake (PEB), and development. If necessary, any additional steps may be added.

The resist composition is first applied onto a substrate on which an integrated circuit is to be formed (e.g., Si, SiO₂, SiN, SiON, TiN, WSi, BPSG, SOG, or organic antireflective coating) or a substrate on which a mask circuit is to be formed (e.g., Cr, CrO, CrON, MoSi, or SiO₂) by a suitable coating technique such as spin coating, roll coating, flow coating, dip coating, spray coating or doctor coating. The coating is prebaked on a hot plate at a temperature of 60 to 150° C. for 10 seconds to 30 minutes, preferably 80 to 120° C. for 30 seconds to 20 minutes. The resulting resist film is generally 0.1 to 2.0 μm thick.

The resist film is then exposed to a desired pattern of high-energy radiation such as UV, deep-UV, EB, x-ray, excimer laser light, γ-ray, synchrotron radiation or EUV (soft x-ray), directly or through a mask. The exposure dose is preferably about 1 to 200 mJ/cm², more preferably about 10 to 100 mJ/cm², or 0.1 to 100 μC/cm², more preferably 0.5 to 50 μC/cm². The resist film is further baked (PEB) on a hot plate at 60 to 150° C. for 10 seconds to 30 minutes, preferably 80 to 120° C. for 30 seconds to 20 minutes.

Thereafter the resist film is developed in an aqueous solution of cyclic ammonium hydroxide according to the invention for a time of 1 to 300 seconds, preferably 3 to 100 seconds at a temperature of 0 to 30° C., preferably 5 to 25° C., to form a resist pattern.

After the development, the resist film may be rinsed, typically with pure water and dried, typically spin dried. Rinsing with surfactant-containing water is acceptable because it is effective for reducing the stress applied to the pattern during spin drying, thus mitigating pattern collapse. Pure water may be replaced by supercritical carbon dioxide because carbon dioxide can be vaporized from the solid state without passing the liquid state. This means that drying takes place under essentially no surface tension. Then pattern collapse is substantially eliminated. However, a special chamber is necessary for creating the high-pressure supercritical state, leading to an outstanding drop of throughput.

EXAMPLE

Examples and Comparative Examples are given below for further illustrating the invention, but they should not be construed as limiting the invention thereto. Mw is a weight average molecular weight as measured by GPC versus polystyrene standards, and Mw/Mn designates molecular weight distribution or dispersity. All parts (pbw) are by weight.

Examples and Comparative Examples Preparation of Developer

Developers #1 to #6 were prepared according to the formulation shown in Table 1.

TABLE 1 Cyclic ammonium hydroxide Surfactant Water Developer (pbw) (pbw) (pbw) #1 1-butyl-1-methylpyrrolidinium hydroxide — (95.84) (4.16) #2 1-propyl-1-methylpyrrolidinium hydroxide — (96.21) (3.79) #3 1-butyl-1-methylpiperidinium hydroxide Acetylene Alcohol 1 (95.48) (4.52) (0.1) #4 1-propyl-1-methylpiperidinium hydroxide — (95.84) (4.16) #5 mepiquathydroxide — (96.57) (3.43) #6 1- (2-phenylethyl)-1-methylpiperidinium hydroxide — (94.22) (5.78)

Preparation of Resist Composition

A positive resist composition in solution form was prepared by dissolving a resist polymer synthesized by the standard radical polymerization process (shown below) in a solvent in accordance with the formulation of Table 2 and filtering through a filter with a pore size of 0.2 μm.

EUV Lithography Patterning Test

On a silicon substrate having a diameter of 4 inches, a silicon-containing SOG film of SHB-A940 (Shin-Etsu Chemical Co., Ltd.) was formed to a thickness of 35 nm. The positive resist composition was coated on the SOG film and prebaked on a hot plate at 110° C. for 60 seconds to form a resist film of 35 nm thick. The resist film was exposed to EUV through a pseudo phase-shift-mask (PSM) in an exposure tool (NA 0.3), baked (PEB) at the temperature shown in Table 3, developed in a developer as shown in Table 1 for 30 seconds, rinsed with pure water or Extreme 10 (AZ Electronic Materials), and spin dried, forming a resist pattern. Sensitivity is the dose at which a 20-nm line-and-space pattern was formed. Maximum resolution is the minimum size which was resolved at that dose. The pattern was measured for edge roughness (LWR) under SEM. The results are shown in Table 3. It is noted that the maximum resolution is determined by pattern collapse, meaning that as the maximum resolution becomes higher, pattern collapse is unlikely to occur.

TABLE 2 Polymer PAG Quencher Surfactant Solvent (pbw) (pbw) (pbw) (pbw) (pbw) Resist 1 Resist — Quencher 1 FC-4430 PGMEA(2,000) material Polymer 1 (1.30) (0.001) PGME(1,000) (100) cyclohexanone(3,000) 2 Resist — Quencher 1 FC-4430 PGMEA(2,000) Polymer 2 (1.30) (0.001) PGME(1,000) (100) cyclohexanone(3,000) 3 Resist — Quencher 1 FC-4430 PGMEA(2,000) Polymer 3 (1.30) (0.001) PGME(1,000) (100) cyclohexanone(3,000) 4 Resist — Quencher 1 FC-4430 PGMEA(2,000) Polymer 4 (1.30) (0.001) PGME(1,000) (100) cyclohexanone(3,000) 5 Resist — Quencher 1 FC-4430 cyclopentanone(1,000) Polymer 5 (1.30) (0.001) cyclohexanone(5,000) (100) 6 Resist PAG 1 Quencher 2 FC-4430 PGMEA(4,000) Polymer 6 (30) (5.00) (0.001) cyclohexanone(2,000) (100) 7 Resist — Quencher 1 FC-4430 cyclopentanone(1,000) Polymer 7 (1.30) (0.001) cyclohexanone(5,000) (100) 8 Resist PAG 2 Quencher 1 FC-4430 cyclopentanone(1,000) Polymer 7 (15) (1.50) (0.001) cyclohexanone(5,000) (100) 9 Resist PAG 3 Quencher 3 FC-4430 cyclopentanone(1,000) Polymer 7 (15) (4.30) (0.001) cyclohexanone(5,000) (100) PGMEA: Propylene glycol monomethyl ether acetate PGME: Propylene glycol monomethyl ether FC-4430: fluorochemical surfactant by 3M-Sumitomo Co., Ltd.

TABLE 3 PEB Maximum temp. Rinse Sensitivity resolution LWR Resist (° C.) Developer liquid (mJ/cm²) (nm) (nm) Example 1 Resist 90 Developer #1 pure water 14 18 4.9 material 1 2 Resist 85 Developer #1 Extreme 10 15 16 4.8 material 1 3 Resist 85 Developer #1 Extreme 10 15 16 4.8 material 2 4 Resist 95 Developer #1 Extreme 10 16 16 4.8 material 3 5 Resist 85 Developer #1 Extreme 10 22 17 4.9 material 4 6 Resist 85 Developer #1 Extreme 10 17 17 5.0 material 5 7 Resist 85 Developer #1 Extreme 10 18 17 5.7 material 6 8 Resist 85 Developer #2 Extreme 10 18 18 4.9 material 4 9 Resist 85 Developer #3 Extreme 10 18 17 4.8 material 4 10 Resist 85 Developer #4 Extreme 10 18 17 4.8 material 4 11 Resist 85 Developer #5 Extreme 10 18 17 4.9 material 4 12 Resist 85 Developer #6 Extreme 10 18 15 4.9 material 4 13 Resist 90 Developer #1 Extreme 10 26 16 4.9 material 7 14 Resist 85 Developer #1 Extreme 10 24 16 3.6 material 8 15 Resist 85 Developer #1 Extreme 10 27 16 3.5 material 9 Comparative 1 Resist 85 2.38 wt % pure water 20 20 5.6 Example material 4 TMAH aqueous solution 2 Resist 85 2.38 wt % Extreme 10 20 19 5.2 material 4 TMAH aqueous solution 3 Resist 85 6.77 wt % Extreme 10 21 18 5.9 material 4 TBAH aqueous solution TMAH: tetramethylammonium hydroxide TBAH: tetrabutylammonium hydroxide

Japanese Patent Application No. 2013-123335 is incorporated herein by reference.

Although some preferred embodiments have been described, many modifications and variations may be made thereto in light of the above teachings. It is therefore to be understood that the invention may be practiced otherwise than as specifically described without departing from the scope of the appended claims. 

The invention claimed is:
 1. A developer for photosensitive resist materials comprising a cyclic ammonium hydroxide having the general formula (1):

wherein R¹ and R² each are a straight, branched or cyclic C₁-C₆ alkyl group or C₂-C₁₀ alkenyl or alkynyl group, and R³ is methylene, ethylene, —O—CH₂—, —S—CH₂— or —NH—CH₂—.
 2. The developer of claim 1 wherein the cyclic ammonium hydroxide is selected from the group consisting of 1-butyl-1-methylpyrrolidinium hydroxide, 1-propyl-1-methylpyrrolidinium hydroxide, 1-butyl-1-methylpiperidinium hydroxide, 1-propyl-1-methylpiperidinium hydroxide, and mepiquathydroxide.
 3. The developer of claim 1, further comprising 0.0001 to 5% by weight of an acetylene alcohol having the general formula (AA-1):

wherein R⁴ to R⁷ are each independently C₁-C₂₀ alkyl, R⁸ and R⁹ are each independently C₁-C₁₀ alkylene, a and b are such integers that the sum a+b is 0 to
 60. 4. A pattern forming process comprising the steps of providing a chemically amplified positive resist composition adapted to increase an alkali dissolution rate under the action of acid, and developing the resist composition in an aqueous solution containing an ammonium hydroxide of formula (1) according to claim
 1. 5. The pattern forming process of claim 4 wherein the chemically amplified positive resist composition comprises a polymer comprising recurring units having an acid labile group and recurring units having a hydroxyl and/or lactone ring adhesive group as a base resin.
 6. The pattern forming process of claim 5 wherein the polymer has a weight average molecular weight of 1,000 to 500,000, and the recurring units having an acid labile group are recurring units of at least one type selected from recurring units (a1) and (a2) having a carboxyl or phenolic hydroxyl group substituted with an acid labile group, as represented by the general formula (2):

wherein R¹⁰ and R¹² are each independently hydrogen or methyl, R¹¹ and R¹³ each are an acid labile group, Y¹ is a single bond, a divalent C₁-C₁₂ linking group having at least one of ester, lactone ring, phenylene and naphthylene, a phenylene group or a naphthylene group, Y² is a single bond, ester group or amide group, subscripts a1 and a2 are numbers in the range: 0≦a1≦0.9, 0≦a2≦0.9, and 0<a1+a2<1.0.
 7. The pattern forming process of claim 6 wherein the polymer comprising recurring units of at least one type selected from recurring units (a1) and (a2) having a carboxyl or phenolic hydroxyl group substituted with an acid labile group, represented by the general formula (2), has further copolymerized therein recurring units of at least one type selected from sulfonium salt units (b1) to (b3), as represented by the general formula (3):

wherein R⁰²⁰, R⁰²⁴, and R⁰²⁸ each are hydrogen or methyl, R⁰²¹ is a single bond, phenylene, —O—R⁰³³—, or —C(═O)—Y—R⁰³³—, Y is oxygen or NH, R⁰³³ is a straight, branched or cyclic C₁-C₆ alkylene group, alkenylene group or phenylene group, which may contain a carbonyl (—CO—), ester (—COO—), ether (—O—), or hydroxyl moiety, R⁰²², R⁰²³, R⁰²⁵, R⁰²⁶, R⁰²⁷, R⁰²⁹, R⁰³⁰, and R⁰³¹ are each independently a straight, branched or cyclic C₁-C₁₂ alkyl group which may contain a carbonyl, ester or ether moiety, a C₆-C₁₂ aryl group, a C₇-C₂₀ aralkyl group, or a thiophenyl group, A¹ is a single bond, -A⁰-C(═O)—O—, -A⁰-O— or -A⁰-O—C(═O)—, A⁰ is a straight, branched or cyclic C₁-C₁₂ alkylene group which may contain a carbonyl, ester or ether moiety, A² is hydrogen, CF₃ or carbonyl, Z¹ is a single bond, methylene, ethylene, phenylene, fluorinated phenylene, —O—R⁰³²—, or —C(═O)—Z²—R⁰³²—, Z² is oxygen or NH, R⁰³² is a straight, branched or cyclic C₁-C₆ alkylene, phenylene, fluorinated phenylene, trifluoromethyl-substituted phenylene or alkenylene group, which may contain a carbonyl, ester, ether or hydroxyl moiety, M⁻ is a non-nucleophilic counter ion, subscripts b1, b2 and b3 are numbers in the range: 0≦b1≦0.3, 0≦b2≦0.3, 0≦b3≦0.3, and 0<b1+b2+b3≦0.3.
 8. The pattern forming process of claim 4, wherein the resist composition further comprises at least one of an organic solvent, basic compound, dissolution regulator, and surfactant.
 9. The pattern forming process of claim 4, comprising the steps of applying the resist composition onto a substrate to form a coating, baking, exposing the coating to high-energy radiation, and developing the exposed coating in the developer.
 10. The pattern forming process of claim 9 wherein the high-energy radiation is KrF excimer laser of wavelength 248 nm, ArF excimer laser of wavelength 193 nm, electron beam or soft x-ray of wavelength 3 to 15 nm. 